Process for modifying the dyeing and other properties of cellulosic textile materials



Patented May 1, 19451 UNITED STATE PROCESS FOR MODIFYING DYEING ANDOTHER PROPERTIES OF CELLULOSIC TEXTIIEBIATERIALS James HutchisonMacGregor, Booking, Braintree,

England, assignor Courtaulds Limited.

London, England, a British company No Drawing. Application January 23,1942, Serial In Great Britain December 24,

a Claims. (o1. 8-100) This invention relates to the treatment ofcellulosic textile material for the purpose of imparting to itwool-dyeing properties, and at thesame time giving it a softer silkierhandle and appearance.

It is well known that wool-dyeing properties.

can be imparted to cellulosic material by applying to it a solublecondensate of formaldehyde and urea 0r thiourea or related compounds-such as cyanamide, guanidine, dicyandiamide, dicyan-' diamidine,biguanide, methylurea, or the mixture of urea, biuret, guanidine andcyanuric acid obtained by decomposing urea by heat at about 160centigrade, and then heating the material to a temperature of forinstance 130 to 160 centigrade until the soluble condensate is convertedinto an insoluble condensate. Instead of employing the solublecondensate of formaldehyde and urea or related compound, a mixture ofthese two compounds can be used, although it may be dimcult todistinguish clearly between a'solution containing the two ingredients,and one containing more or less of the soluble condensate, since it isbelieved that as soon as the formaldehyde and urea are put together inaquous solution, reaction commences with at least some formation of thesoluble condensate.-

I have now found that the aflinity of cellulosic textile material forthose dyestuffs used fordveing wool and the like animal fibres "can beincreased and at the same time a softer silkier handle and appearancecan be imparted to they said cellulosic textile material by treating thesaid material with a solution containing formaldehyde and anarylguanidine, either as such or more probably in the form of theirwatersoluble condensate, and then converting the mixture or the solublecondensate into an insoluble condensate,

for instance by heating to a temperature of 140 centigrade in thepresence ofan acid catalyst.

As an example of an arylsuanidine which can be used according tothisinvention I mention diphenylguani v CiHt-NB-C-NH-Cdii Theprocessaccording to this invention can, if desired, be carrled out in thepresence of other watersoluble condensates, such for instance asurea-formaldehyde, thiourea-formaldehyde and melamine-formaldehyde, andit will be found that the presence of the arylguanidineformaldehydecompound improves both the wool-dyeing properties of thecellulosic textile material and also its handle; the fastness to lightof the dyed that a stabilising effect is exerted on the-saidurea-formaldehydecondensate on the additionof an acid'catalyst.When'carrying out the process'of the present invention I have found thatit is desirable to avoid the useof a large excess of formaldehyde. Thefollowing examples illustrate the invention but they are not to beconsidered as limiting it in any way.

' Example 1 30 grams of diphenylguanidine are dissolved by warming with30, cubic centimetres of per cent acetic acid. 160 cubic centimetres of40 per cent formaldehyde are added with sufficient distilled water tomake 1 litre of solution.. A sample of an all viscose satin fabric isimmersed therein andafter saturation the fabric is removed from thesolution and is squeezed evenly so that it contains from to per cent ofits own weightof the liquor. The fabric is then placed on a' pin stenterframe so that it retains its original dimensions, and is dried at justunder 100 centigrade. The fabric is heated at centigrade for 15 minutesto effect the formation of the insoluble condensation product from thediphenylguanidin'e and the formaldehyde. The resultant fabric is thendyed at the boil for 15 minutes with 1 per cent Azo Geranine 208 (ColourIndex No. 31) and 2 per cent formic acid based on the weight of thefabric, in a bath containing a fabric to liquor ratio of 1 to 40. Thefabric is dyed a full shade of red comparable to that obtained withwool. The fabric has a soft silky handle and appearance and the dyedmaterial has an improved fastness to light.

Example! 30 grams of triphenylguanidine hydrochloride and 200 cubiccentimetres of 40 percent formaldehyde are dissolved in sufilcientdistilled water to make 1 litre of solution. A sample of.an all 'viscmsatin fabric is soaked in this solution.

The fabric is removed fromthe solution, squeezed evenly and dried atJust under 100 centigrade Emmple 3 A watersoluble urea-formaldehydecondensate 18 made by mixing together 135 grams of urea, 312 cubiccentimetres of 40 per cent formaldehyde and "19 cubic centimetres ofmethanol, the pH of the solution is adjusted to 9.5 and the solution isboiled under reflux for minutes, after which it is cooled as rapidly aspossible.

grams of di-phenylguanidine are dissolved in 30 cubic centimetres of percent acetic acid and this solution is added to grams of the urea-'formaldehyde condensate prepared above and mixed with suflicientdistilled water to make 1 litre of solution. A sample of, an all viscosesatin fabric is immersed therein and after soaking the fabric is removedfrom the solution and squeezed evenly so'that it contains from 90 to percent of its the said material before dyeing an aqueous solutioncontaining a watersoluble condensate of tion containing formaldehyde andan arylguaniformaldehyde and an arylguanidine and then con.

verting the soluble condensate into an insoluble of an acid catalyst. I

2; The process of increasing the afflnity of cellulosic textile materialfor those dyestuffs used for dyeing wool and the like animal fibers, andimparting a soft silky handle thereto, by treating the said materialbefore dyeing with anaqueous soludine andthe'n converting the mixtureinto an the formaldehyde is split of! from the urea-'formaldehydecondensate and combines with the diphenylguanidine. The formation of theinsoluble condensation product is effected by heating the fabric atcentigrade for 15 minutes. The .fabric is dyed at the boil for'20minutes with 1 per cent Coomassie Violet RS (Colour Index No." 698) and2 per cent'forl nic acid based on weight of the fabric in a'bathcontaining a fabric to liquor ratio of l to 40. The fabric is dyed afullshade of violet. The material is crease-resistant and possesses asuperior handle compared with" insoluble condensate. by drying andheating in the presence of an acid catalyst.

3. As a new article of manufacture, cellulosic textile material which ihas been treated with a solution containing a watersoluble condensate offormaldehyde and an arylguanidine, said watersoluble condensatethereafter being converted into aninsoluble condensate, by drying andheating in the presence of an acid catalyst.

solution containingformaldehyde and an arylj guanidine,saidmixttirethereafter being converted into an insoluble condensate, bydrying and heating inthe presence of an acid catalyst.

' 5. The process of increasing the affinity of 5 cellulosic textilematerials for those dyestufls used for dyeing wool and the like animalfibres, and imparting a soft, siikyhandle thereto,including fabric whichhas been impregnated flar s n formaldehyde alone. r If desired, awatersoluble diphenylguanidineformaldehyde condensate may be substitutedfor thediphenylguanidine in this example. What I claim is:.

l. The process of increasing the aflinity of cellu-' ,losic textilematerial for those dyestuffs used for dyeing wool and the like animalfibers, and imparting a soft silky handle thereto, by treating a ent No.2,575,121

was aurcnrsoanaeonseoa. a It is hereby certified that error appears inthe printed specification treathig the" material before dyeing with anaqueouss'olutio'n selected from the group consisting of a solution offormaldehyde and anarylguanidine, a and a solution of a water-solublecondensate of 1 formaldehyde and an arylguanldine, and thererial inpresence of an. acid catalyst.

JAB. 'n. mcaamon.

of the above mambered patent requiring correction as follows: Page-2second column, line 17, 3,and line 21 claim for "with a read h naqueous--; and that the said Letters 'Patent shouid'beread with i thiscorrection therein that the same may conform to the record "in thePatent Office.

' i signed and sealed this fin r 9 e 9 5 Leslie Frazer actingCommissioner of Patents.

Emmple 3 A watersoluble urea-formaldehyde condensate 18 made by mixingtogether 135 grams of urea, 312 cubic centimetres of 40 per centformaldehyde and "19 cubic centimetres of methanol, the pH of thesolution is adjusted to 9.5 and the solution is boiled under reflux forminutes, after which it is cooled as rapidly as possible.

grams of di-phenylguanidine are dissolved in 30 cubic centimetres of percent acetic acid and this solution is added to grams of the urea-'formaldehyde condensate prepared above and mixed with suflicientdistilled water to make 1 litre of solution. A sample of, an all viscosesatin fabric is immersed therein and after soaking the fabric is removedfrom the solution and squeezed evenly so'that it contains from 90 to percent of its the said material before dyeing an aqueous solutioncontaining a watersoluble condensate of tion containing formaldehyde andan arylguaniformaldehyde and an arylguanidine and then con.

verting the soluble condensate into an insoluble of an acid catalyst. I

2; The process of increasing the afflnity of cellulosic textile materialfor those dyestuffs used for dyeing wool and the like animal fibers, andimparting a soft silky handle thereto, by treating the said materialbefore dyeing with anaqueous soludine andthe'n converting the mixtureinto an the formaldehyde is split of! from the urea-'formaldehydecondensate and combines with the diphenylguanidine. The formation of theinsoluble condensation product is effected by heating the fabric atcentigrade for 15 minutes. The .fabric is dyed at the boil for'20minutes with 1 per cent Coomassie Violet RS (Colour Index No." 698) and2 per cent'forl nic acid based on weight of the fabric in a'bathcontaining a fabric to liquor ratio of l to 40. The fabric is dyed afullshade of violet. The material is crease-resistant and possesses asuperior handle compared with" insoluble condensate. by drying andheating in the presence of an acid catalyst.

3. As a new article of manufacture, cellulosic textile material which ihas been treated with a solution containing a watersoluble condensate offormaldehyde and an arylguanidine, said watersoluble condensatethereafter being converted into aninsoluble condensate, by drying andheating in the presence of an acid catalyst.

solution containingformaldehyde and an arylj guanidine,saidmixttirethereafter being converted into an insoluble condensate, bydrying and heating inthe presence of an acid catalyst.

' 5. The process of increasing the affinity of 5 cellulosic textilematerials for those dyestufls used for dyeing wool and the like animalfibres, and imparting a soft, siikyhandle thereto,including fabric whichhas been impregnated flar s n formaldehyde alone. r If desired, awatersoluble diphenylguanidineformaldehyde condensate may be substitutedfor thediphenylguanidine in this example. What I claim is:.

l. The process of increasing the aflinity of cellu-' ,losic textilematerial for those dyestuffs used for dyeing wool and the like animalfibers, and imparting a soft silky handle thereto, by treating a ent No.2,575,121

was aurcnrsoanaeonseoa. a It is hereby certified that error appears inthe printed specification treathig the" material before dyeing with anaqueouss'olutio'n selected from the group consisting of a solution offormaldehyde and anarylguanidine, a and a solution of a water-solublecondensate of 1 formaldehyde and an arylguanldine, and thererial inpresence of an. acid catalyst.

JAB. 'n. mcaamon.

of the above mambered patent requiring correction as follows: Page-2second column, line 17, 3,and line 21 claim for "with a read h naqueous--; and that the said Letters 'Patent shouid'beread with i thiscorrection therein that the same may conform to the record "in thePatent Office.

' i signed and sealed this fin r 9 e 9 5 Leslie Frazer actingCommissioner of Patents.

